Office europeen des brevets (fi) Publication number : 0 555 050 A1
@ EUROPEAN PATENT APPLICATION
@ Application number : 93300752.8 @ Int. CI.5 : C08G 77/06, C08L 83/04
(22) Date of filing : 02.02.93
(So) Priority : 06.02.92 US 832065 @ Inventor : Traver, Frank John 1 Downey Road Troy, New York 12180 (US) (43) Date of publication of application : Inventor : Ward, Brian John 11.08.93 Bulletin 93/32 R.D. 1, Box 236 Valley Falls, New York 12185 (US) Inventor : Delker, Wayne Lee @) Designated Contracting States : 1 Imperial Court DE ES FR GB IT NL Ballston Lake, New York 12019 (US) Inventor : Thimineur, Raymond Joseph 162 Willow Lane @ Applicant : GENERAL ELECTRIC COMPANY Scotia, New York 12302 (US) 1 River Road Schenectady, NY 12345 (US) (74) Representative : Pratt, Richard Wilson et al London Patent Operation G.E. Technical Services Co. Inc. Essex House 12/13 Essex Street London WC2R 3AA (GB)
(54) Liquid silicone copolymers.
(57) A process for the production of liquid copolymers having R3SiO05 units and Si02 units comprises reacting a hydrolyzable triorganosilane with an alkyl orthosilicate in the presence of water and an aliphatic hydrocarbon solvent having from 6 to 15 carbon atoms and an aromatic hydrocarbon content of less than 0.5 percent by weight based on the total weight of the solvent.
< O IO o 10 10 10 o Q_ LU Jouve, 18, rue Saint-Denis, 75001 PARIS EP 0 555 050 A1
The present invention relates to the production of a novel family of liquid copolymers having R3SiO0.5 units and Si02 units. More particularly the present invention relates to copolymers, commonly known as MQ resins, which are produced in novel liquid form by a hydrolys is reaction in an aliphatic hydrocarbon solvent having from 6 to 15 carbon atoms. Such polymers have substantial utility in compositions in which solid counterparts 5 prepared in aromatic solvents would not be suitable, especially in personal care products.
BACKGROUND OF THE INVENTION
Silicone materials are well-known and are highly regarded for their high temperature capabilities, for their 10 resistance to the elements and for their good low temperature properties. In addition, silicon compositions are good electrical insulating materials. Resinous copolymers composed of R3SiO0.5 units and Si02 units are well known in the art and are descri- bed in, for example, Dexter, United States Patent No. 2,736,721; Currie, United States Patent No. 2,814,601; Goodwin, United States Patent No. 2,857,356; and Modic, United States Patent No. 3,205,283. These copo- 15 lymers are prepared by hydrolyzing a hydrolyzable triorganosilane, such as trimethylchlorosilane, with an alkyl orthosilicate, such as ethyl orthosilicate, or the partial hydrolyzate of such alkyl orthosilicate. The hydrolysis is generally conducted in the presence of a small amount of water and in the presence of a suitable aromatic organic solvent, such as toluene or xylene. These resin copolymers are in the form of a solid resin product and have been found to be useful in many 20 commercial applications. They have been reported to be useful in the preparation of high strength organopo- lysiloxane compositions. See, Jeram et al., United States Patent No. 3,884,866. Their use in preparing room temperature vulcanizable (RTV) silicone rubbers has also been noted, such as in Smith, United States Patent No. 4,490,500. Saad, United States Patent No. 4,247,441 teaches preparing silicone molding compositions having excellent electrical properties. The use of the silicone resin copolymers inadhesive compositions is also 25 well known in the art and is described in Horning, United States Patent No. 4,016,328; and Blizzard, United States Patent No. 4,255,316. More recently, such copolymer resins are finding use in personal care products, i.e., in compositions for use on the skin, e.g., as antiperspirants, sunscreens, lotions, and the like. However, the use of toluene and other aromatic hydrocarbons as the solvent in the synthesis of the silicone 30 copolymers has increasingly become a concern because trace amounts of aromatic hydrocarbons such as tol- uene in the product resin requires special labelling, especially for personal care products, and in some instanc- es there is a very low tolerance level for aromatic residues. It has therefore become necessary to find a re- placement for toluene as a solvent in the hydrolyzation process to produce silicone copolymers. Further, the prior art silicone copolymers are produced in a powdery form which requires the addition of 35 solvents in order to affix the powdery silicone copolymers with silicone fluids. These solvents must then be removed. It would therefore represent an advance in the art if a silicone copolymer could be prepared having increased solubility in silicone fluids. Still further, the prior art silicone copolymers do not dissolve readily in higher viscosity fluids. This detri- mental characteristic further limits the use of these copolymers in personal care compositions such as skin 40 lotions and sunscreeens. It has now been surprisingly found that by employing an aliphatic hydrocarbon of from 6 to 15 carbon atoms as the solvent for the hydrolyzation reaction, a novel silicone copolymer is produced in the liquid form which is substantially free from any aromatic hydrocarbons and which has improved solubility in silicone resin fluids and other solvents. Unexpectedly, as shown in the working examples of the instant specification, these novel 45 silicone copolymers can be dissovled in high proportions in high molecularweightfluids. this excellent property provides a formulating flexibility to the end user, enabling the preparation of protective skin care products.
SUMMARY OF THE INVENTION
50 According to the present invention there is provided a novel liquid silicone copolymer substantially free from any aromatic hydrocarbon impurities comprising R3SiO0.5 units and Si02 units wherein R is a monovalent hydrocarbon radical selected from the group consisting of alkyl radicals of from 1 to 8 carbon atoms, alkenyl radicals of from 1 to 8 carbon atoms, cycloalkyl radicals, mononuclear aryl radicals and haloalkyl radicals, pre- pared by a process comprising hydrolyzing a hydrolyzable triorganosilane with an alkyl orthosilicate in the pres- 55 ence of water and an aliphatic hydrocarbon of from 6 to 1 5 carbon atoms having an aromatic hydrocarbon con- tent of less than 0.5 percent by weight based on the total weight of the solvent. Preferably the aliphatic hydrocarbon solvent comprises n-hexane, the alkyl orthosilicate comprises ethyl orthosilicate, the hydrolyzable triorganosilane comprises trimethylchlorosilane, and the liquid copolymer com- 2 EP 0 555 050 A1
prises from about 0.5 to about 1.0 R3SiO0.5 units per Si02 units. Also according to the present invention there is disclosed an improved process for preparing a silicone copolymer comprising R3SiO0.5 units and Si02 units wherein R is a monovalent hydrocarbon radical selected from the group consisting of alkyl radicals of 1 to 8 carbon atoms, alkenyl radicals of 1 to 8 carbon atoms, cy- 5 cloalkyl radicals, mononuclear aryl radicals and haloalkyl radicals comprising hydrolyzing a hydrolyzable trior- ganosilane with an alkyl orthosilicate in the presence of water, the improvement comprising carrying out the hydrolyzation reaction in the presence of an aliphatic hydrocarbon solvent of from 6 to about 15 carbon atoms having an aromatic hydrocarbon content of less than 0.5 percent by weight based on the weight of the solvent, wherein said copolymer is in the liquid form and is substantially free of any aromatic hydrocarbon impurities. 10 Substantially free is defined for purposes of the present invention as having less than trace amounts of the impurity.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
15 The present invention provides novel liquid silicone copolymers, also known as MQ resins, having R3SiO0.5 units and RSi02 units. These copolymers are prepared by hydrolyzing a hydrolyzable triorganosilane with an alkyl orthosilicate orthe partial hydrolyzate of such alkyl orthosilicate in the presence of water and an aliphatic hydrocarbon solvent having from 6 to about 15 carbon atoms having an aromatic hydrocarbon content of less than 0.5 percent by weight based on the total weight of the solvent. During the cohydrolysis of the triorgano- 20 silane and alkyl orthosilicate, most of the silicon bonded halogen and the silicon bonded alkoxy groups are replaced by silicon-bonded hydroxyl groups through which the two organosilicon materials condense to form siloxane linkages. The liquid copolymer is generally soluble in the organic aliphatic hydrocarbon solvent and insoluble in the water present in the hydrolysis reaction system, and the organic aliphatic hydrocarbon layer therefore contains the resinous copolymer. This organic solvent layer containing the liquid copolymer is sepa- 25 rated from the aqueous layer and in some cases washed several times with water to provide the liquid copo- lymer in the organic aliphatic hydrocarbon solvent relatively free of either hydrochloric acid which results from the hydrolysis of the alkanol which results from the hydrolysis. The aliphatic hydrocarbon solvent used in the hydrolysis reaction which forms the resinous copolymer can vary within wide limits. Typically they comprises aliphatic hydrocarbons having from 6 to about 15 carbon 30 atoms. Preferred are hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, isomers thereof and mixtures of any of the foregoing. Most preferred is n-hexane. These materials are well known to those skilled in the art and are available commercially. Also preferred for use in the present invention are the isoparaffinic aliphatic solvents. A particulary pre- ferred commercial isoparaffinic aliphatic solvent is lsopar®E, Exxon Corporation, which is an isoparaffinic sol- 35 vent of principally C8 isomers. Other preferred commercial solvents are lsopar®C, G, H, K, L and M which are all isoparaffinic aliphatic solvents, the latter comprising a mixture of mainly C13-C16 isomers. Important to the present invention is that the aliphatic hydrocarbon solvent have an aromatic hydrocarbon, such as benzene, toluene, styrene and xylene, content of less than 0.5 percent by weight based on the weight of the solvent. Preferably, the aromatic hydrocarbon content in the solvent is less than 0.2 percent by weight. 40 The R3SiO0.5 units present in the resinous copolymer are generally those in which the R groups are methyl groups. However, also applicable are those units wherein the R groups are other monovalent hydrocarbon rad- icals such as, for example, alkyl radicals, e.g., ethyl, propyl, butyl, octyl, etc. radicals, aryl radicals, e.g., phenyl, naphthyl, xylyl, tolyl, etc., aralkyl radicals, e.g., benzyl, phenylethyl, etc. radicals, alkenyl radicals, e.g., vinyl, allyl, etc. radicals and cyclic hydrocarbon radicals, e.g., cyclohexyl, cycloheptyl, cyclohexenyl etc. radicals, and 45 various halogenated monovalent hydrocarbon radicals including chloromethyl, chloropropyl, dibromophenyl, etc. radicals. Preferably, where radicals other than methyl radicals are included in the R3SiO0.5 units, the units also contain at least 50 percent trimethylsiloxane units. The alkyl orthosilicates employed in the practice of the present invention are generally of the formula: (R'0)4Si so where R' is a lower alkyl radical or a lower hydroxy alkyl radical, such as methyl, ethyl, propyl, butyl, octyl, hydroxy ethyl, etc. radicals. Preferably, the alkyl orthosilicate employed is ethyl orthosilicate orthe partial hy- drolysis product thereof. The methods of conducting the hydrolysis reaction is well known to those skilled in the art and is described in the patent literature. It is essential however for the purposes of the present invention that the solvent em- 55 ployed comprise an aliphatic hydrocarbon having an aromatic hydrocarbon content of less than 0.5 percent by weight based on the weight of the solvent. The resulting copolymer is in the liquid form and has a ratio of R3SiO0.5 units to Si02 units of from about 0.5 to about 2.0, more preferably from about 0.6 to about 1 .0. The liquid copolymers have been found to exhibit 3 EP 0 555 050 A1
many important properties over the solid copolymers of the prior art, including no trace amounts of aromatic hydrocarbon impurities, better solubility in silicone fluids and other solvents and an increased viscosity in sil- icone fluids. As will be seen in the working examples which follow, different and unexpected advantages are obtained 5 in back-to-back comparisons wherein the liquid copolymers of the present invention are formed into useful compositions and compared with compositions prepared with the solid copolymers of the prior art. In one major end use aspect of the invention, the liquid copolymers are added to a silicone fluid such as an M-stopped diorganopolysiloxane fluid. However, it in also contemplated that silanol end-stopped diorgano- polysiloxane fluids can be used in the practice of the present invention. Such compositions are broadly useful 10 to produce, for example, potting compounds effective to protect electronic components, for producing the so- called room temperature vulcanizing (RTV) silicone compositions used for caulking and sealing, and for per- sonal care compositions such as skin lotions and sunscreens. Preferred silanol end-stopped polymers are of the general formula:
15 HO
20 where R4 and R5 are the same or different and are monovalent hydrocarbon radicals, where n varies so that the polymer has a viscosity varying from 100 to 4,000 centipoise at 25°C. Preferably, the polymer has a vis- cosity ranging from 100 to 2,000 centipoise at25°C. The R4and R5 radicals can be any of the radicals selected from the group of alkyl radicals, such as methyl, ethyl, propyl, etc.; cycloalkyl radicals, such as cyclohexyl, cy- 25 cloheptyl, etc.; alkenyl radicals such as vinyl, allyl, etc.; mononuclear aryl radicals such as phenyl, methylphe- nyl, ethylphenyl, etc.; and haloalkyl radicals such as fluoropropyl radicals including 3,3,3-trifluoropropyl, etc. The silanol end-stopped polymer can be a polymer of substantially one viscosity or it may be a blend of two polymers of different viscosities to a arrive at a final silanol end-stopped polymer blend that has a viscosity varying from 100 to 4,000 centipoise at 25°C. 30 Accordingly, the silanol polymer can be a blend of two or more silanol diorganopolysiloxane polymers wherein one of the silanol polymers has a viscosity in the range of 1,000 to 10,000 centipoise at 25°C, and wherein the second silanol polymer has a viscosity in the range of 10 to 1,500 centipoise at25°C. Furthermore, there can beany other polymers present which have a viscosity in the range of 100 to 4,000 centipoise at25°C. It is only necessary that the final polymer blend have a viscosity ranging from 1 00 to 4,000 centipoise at 25°C. 35 In certain embodiments of the present invention solutions of the novel copolymers of the present invention and the silanol end-stopped polymers are prepared in proportions ranging from about 20 to about 60 weight percent of copolymer and from about 80 to about 40 weight percent of silanol end-stopped polymer. Preferred are solutions comprising from about 40 to about 60 weight percent of copolymer and from about 60 to about 40 weight percent of silanol end-stopped polymer. 40 The silanol polymer is produced either by a batch process or a continuous process. One method of pro- ducing a silanol polymer is to take the appropriate organopolysiloxanes and equilibrate them by reacting them in the presence of small amounts of potassium hydroxide catalyst at elevated temperatures, that is about 1 00°C and more preferably at temperatures above 150°C. At that temperature, the cyclopolysiloxane such as octa- methyltetracyclo polysiloxane is equilibrated along the appropriate amount of chainstoppers, such as for in- 45 stance water or a low molecular weight silanol terminated diorgano-polysiloxane, to form a silanol endstopped diorganopolysiloxane polymer. The most preferred chain stopper is water since it is cheaper and is quite ef- fective especially in the continuous processes. The amount of water is determined by the viscosity of the di- organopolysiloxane polymer that is desired or the molecular weight of the end product diorganopolysiloxane product that is desired. Upon being equilibrated, the cyclo polysiloxane forms the silanol end-stopped diorga- 50 nopolysiloxane polymer. At that point, the mixture is cooled, the catalyst is neutralized with phosphoric acid or a silyl phosphate and then the mixture is heated at elevated temperatures to remove unreacted cyclics. It should be noted that in a continuous process for producing the silanol end-stopped diorganopolysiloxane polymer or a blend of polymers, that the mixture is not cooled before it is neutralized, and indeed it does not have to be so cooled, since the polymer mixture has to be heated at temperatures above 50°C to remove the 55 unreacted cyclics from the polymer mixture. It should be further noted that the process for preparing the silanol end-stopped polymer is set forth among other places in Bessmer et al. United States Patent No. 3,888,815 which is hereby incorporated by reference. However, there are other processes for preparing such silanol end-stopped polymers. 4 EP 0 555 050 A1
The liquid copolymers and the silanol end-stopped polymers are mixed together in any convenientfashion. It is found that the liquid copolymers and the silanol end-stopped polymers are completely miscible so that a uniform homogeneous solution of the liquid copolymers and the silanol end-stopped polymers is obtained upon mixing. Preferably, the mixture comprises from 1 to 10 parts by weight of the silanol end-stopped polymer per 5 part by weight of liquid copolymer. It is also contemplated that the liquid copolymers can be dissolved in organic solvents prior to admixing with the silanol end-stopped polymers. Where a solvent is used, it is important to remove the organic solvent from the solution. This can be effected by heating the solution under a reduced pressure as is well known to those skilled in the art. It is necessary to remove substantially all of the solvent from the solution. 10 While the exact chemical structure of this resulting solventless fluid material is not known with certainty, it is known that the solution contains a number of silicon-bonded hydroxyl groups or silanol groups. In general, the hydroxyl groups comprise from about 0.1 to 3 percent by weight of the total solventless fluid. The presence of these silicon-bonded hydroxyl groups in the solventless fluid provide reactive sites through which the fluid can be cured after it is cast about an article to be encapsulated. These encapsulating fluids can be cured with 15 either acidic or basic catalysts. Of the acidic catalysts which can be employed to effect curing can be mentioned, for example, the metal salts of organic carboxylic acids and in particular the organic carboxylic acid salts of metals such as lead, tin, zinc, iron, cobalt, chromium, manganese, etc. The organic carboxylic acid portion of these salts include any of the well known organic carboxylic acids which in their metal salt form, are conventionally used as paint driers. 20 These acid derivatives include the acetates, octoates, butyrates, naphthanates, etc. Among the preferred met- al salt curing agents can be mentioned, for example, zincoctoate, lead acetate, lead octoate, lead naphthanate, and dibutyl tin dilaurate. Where these metal salt curing agents are employed, they are used in an amount equal to from about 0.01 to 2 percent by weight of the metal from which the metal salt is derived. Among the basic materials which can be employed as curing agents for the solventless encapsulating flu- 25 ids of the present invention are quaternary ammonium and quaternary phosphonium compounds such as tet- ramethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, tetrabutyl phosphonium hydroxide, etc. Other preferred catalysts are those comprising a primary, secondary or tertiary amine and an epoxy-containing organic compound as are known to those skilled in the art. The primary, secondary or tertiary organic amines are those such as 1,3-di-methylbutyl amine, dimethyl soya amines, dibutyl benzyl amine, tetramethyl guani- 30 dine, M-methylmorpholine, tri-ethanol amine and dibutyl amine. The epoxy compounds employed in this cat- alyst system include the glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, the diglycidyl ether of bis-1 ,3-hydroxypropyl tetramethyldisiloxane, styrene oxide, cyclohexane oxide, as well as resinous materi- als containing epoxy groups such as the resinous reaction product of epichlorohydrin and p,p'-dihydroxyphe- nyldimethylmethane. Where this curing catalyst comprising the amine and epoxy compound is employed, both 35 the amine and the epoxy compound are employed in an amount equal to from about 0.1 to about 5 percent by weight based on the weight of the solventless encapsulating fluid with the ratio of the amine compound to the epoxide compound being sufficient to provide from about 0.2 to 5 moles of the amine per mole of the epoxy compound. The choice of the particular catalyst which will be employed to cure the solventless encapsulating fluids 40 of the present invention will depend on a number of factors. For example, while the metal salt curing agents provide very satisfactory cure of the encapsulating fluids, it is found that the acid residue from the curing cat- alyst has an adverse affect on certain metal parts, such as copper parts. Thus, when a printed circuit board having copper surface elements is encapsulated in the fluid of the present invention which has been catalyzed with a metal salt it is found that the acid residue tends to tarnish or discolor the copper elements, thereby ad- 45 versely affecting both the appearance and the performance of such copper elements. On the other hand, when the material to be encapsulated is already enclosed in some other material, or is formed from a material such as stainless steel, the acid residue from the metal salt catalysts have no adverse affect on the curing system. The quaternary ammonium compound curing catalysts also present certain problems. These materials are so active that an extremely rapid cure of the solventless encapsulating system occurs resulting in a problem of so bubble formation in the encapsulating coating. This can be reduced by lowering the concentration of the cat- alyst but again, this results often in an uneconomical rate of cure. On the other hand, the aforementioned amine/epoxy two component catalyst system has been found ideally suitable to the curing of the solventless encapsulating solution of the present invention with the rate of cure being suitable so that both thin sections and extremely thick sections, such as section two or more inches thick, can be cured at a fairly rapid rate with- 55 out the formation of bubbles in the resulting materials. The copolymers of the present invention can also be employed in preparing two component room temper- ature vulcanizable silicone rubber composition which are well known to those skilled in the art and are descri- bed in the literature, e.g. United States Patent No. 4,490,500. 5 EP 0 555 050 A1
The copolymers of the present invention can also be employed in preparing fluid/resin blends, used in per- sonal care products, such as protective skin lotions and sunscreens, which are well known to those skilled in the art and are described in the literature.
5 DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following examples illustrate the present invention only. The examples are not intended to limit the scope of the present invention in any manner.
10 EXAMPLES 1 and 2
A blend was prepared in a beaker from 395.8 g of triorganosilane and 204.7 g of hexane (Exxon Low Odor Paraffin Solvent). 553.7 g of the blend was then added to 700.3 g of ethyl silicate with agitation. To the mixture was added 15 450.3 g of city water using a dripping funnel. The boiling point of hexane is 67°C, so the water was added very slowly. During addition, the batch started refluxing so water addition was discontinued until refluxed stopped and temperature was about 50°C. Water was added again very slowly, keeping temperature at 55°C until about 20 to 30 g were left and the batch began to become very viscous. After discontinuing stirring and water addition, separation of the batch 20 occurred with no gelling. The remaining water was added and stirring was continued for 15 minutes. A trace of Chicago blue dye was added. The batch was then transferred to a large separatory funnel and was allowed to separate for about 1 hour, at which time the lower layer was removed and the upper layer discarded. The hydrolyzate was then stripped to remove solvent by gradually increasing heat to cause solvent to distill, 25 for about 60 minutes at from 45 to 80°C until no solvent remained. The batch was then cooled and the resin was transferred to a glass jar. There resin was liquid with a slight cloudiness and yellow tint. The viscosity of the product resin was 68.5 cps as measured on a Spindle No. 1 viscometer, speed 20 rpm and temperature of23.0°C. The same procedure is then followed, except that the hexane solvent is replaced with lsopar®E (Exxon 30 Corporation) isoparaffinic solvent of principally C8 isomers having a total aromatic content of 0.02% by weight. For comparative purposes, the procedure is followed using toluene as the solvent. The three samples are then added to a diluent, polydimethylsiloxane, SF1 8-350 in Examples 1 and 2, and SF96-350 in comparative Example 1A*, in varying amounts for solubility testing. The results are set forth below in Table 1 . 35
TABLE 1 Example 1A» I 2 Solvent 40 Toluene Hexane Isopar* E Viscosity* 100% Resin Solid 56/000 1,284,000 60% Resin 3,840,000 820 1,180 35% Resin 1,500 650 550 20% Resin 550 45 566 450 % Silanol 1-24 0.29 % Alkoxy 5.0 - Comparative Example 50 a ■ centipoise, percent of resin in SF 350 diluent
From Table 1 above, it can readily be seen that the MQ resine manufactured in aliphatic hydrocarbons, hexane and-lsopar® E, have vastly increased solubility in 350 weight silicone fluids over MQ resins manufac- 55 tured in toluene.
6 EP 0 555 050 A1
EXAMPLES 3-10
Three different MQ resins were dispersed in a polydimethyl siloxane fluid at varying concentration. The first resin, comparative examples 3A*, 3B* and 30, has a 0.67:1 M:Q ratio and was made in toluene; the sec- ond resin, examples 3-6, has a 0.67:1 M:Q ratio and was made in n-hexane; and the third resin, examples 7- 10, has a 1 :1 M:Q ratio and was made in n-hexane. The respective resins are tested for viscosity, appearance and water resistance. The results are set forth below in Table 2. EP 0 555 050 A1
a 2G 04 tN
s in
0O| x o VO
I—t
vol s a CN m m
mi s in m O vo
•
of the resins prepared in toluene were run since the resin is a solid. It can be clearly seen from the data in Table 2 above, that much greater amounts of copolymer made in hexane can be dissolved in the high molecular weight fluid (SF-96(350)). Excellent viscosities are obtained using 60 percent of the copolymers of the present invention, whereas suitable viscosities could only be obtained with 35 percent of the prior art copolymers. 5 The ability of the higher percentages of the copolymers of the present invention to be dissolved in high molecular weight silicone fluids allows the preparation of personal care compositions having less tackiness and which enable protective skin care formulations to be prepared.
EXAMPLES 11-13 10 Water Resistance (Substantivity) of Resins.
Water resistance tests were run by employing a spray test method according to the following. A six inch glass laboratory funnel was held above the test specimen on a laboratory ring stand by a laboratory ring sup- 15 port. Aspray nozzle of 1 7/16 inch outside diameter having a convexface with a 1 1/4 inch radius was connected to the funnel bottom with piece of 3/8 inch rubber tubing. The nozzle was provided with 1 9 holes, each 0.035 inch in diameter, having one hole in the center, 6 evenly spaced holes on a 25/64 inch diameter circle, and 12 evenly spaced holes on a 27/32 inch diameter circle concentric with the outside circumference of the nozzle. The distance from the top of the funnel to the bottom of the nozzle was 7.5 inches. A Lexan® sheet 6" wide 20 was placed under the the nozzle at a distance of 6 inches, and held at a 45° angle. Two samples were run side by side using 3/4" wide masking tape to separate as follows. Either 100cc or 250cc aliquots of water were used in testing the water resistance. The test was run until one sample failed by nearly all of the film washing off or until a total of 2000cc of water was used. Six drops of the test material was placed on the area for samples and spread in a thin film with a fingertip. The samples 25 10 and 1 0A* were first cut in SF1202 (pentamer) at 50% solution because of viscosity, and applied in the same manner. The SF1202, being volatile, was allowed to evaporate before testing began. The results are set forth in Table 3 below.
TABLE 3 Example 11A* 11 12A* 12 13A* 13 Copolymer 35* 35b 35* 60° 60d 100* Solvent T H T H T H Comments L M E E E E
* - Comparative Example * = Example 3B* copolymer = Example 5 copolymer 40 c = Example 4 copolymer d = Example 3A* copolymer * = Example 3 copolymer T = Toluene solvent 45 H = Hexane solvent L = 1/2 left after 6 cycles of wash M = Failed after 4 cycles E ~ Examples 12 A* and 12; and examples 13A* and 13 exhibited equivalent performance, respectively. 50 In all cases, higher resin levels of hexane produced resin were required to give comparable water resis- tance results.
EXAMPLE 14 55 In order to determine the effect of common ingredients with the MQ resin products, a series of the resins was formulated into a sunscreen formulation which is expected to give an SPF value from 4 to 8. The formual- tions and their water resistance results, as described above, are set forth in Table 4 below. All samples were 9 EP 0 555 050 A1
dried for 2 hours before testing.
TABLE 4 s Example 14A* 14B* 14C* 14 Composition, pbw Part A Stearic Acid 2.5 2.5 2.5 2.5 10 Cetyl Alcohol 1.8 1.8 1.8 1.8 Amphisol«* 2.5 2.5 2.5 2.5 Copolymer 3.0 3.0 6.0 3.0 2-Ethylhexyl p-methoxycinnamate 7.5 7.5 7.5 7.5 15 SF-1202d 10.0 10.0 7.0 10.0
Part B Glycerine 3.0 3.0 3.0 3.0 Keltrol T»* 0.3 0.3 0.3 0.3 20 Water 69.4 69.4 69.4 69.4
Water Resistance
Rating 0 ++ +++ + ?5 * Comparative Example « Givaudan Corp. b Example 13A* copolymer e 50% MQ resin of Example 13 A* and 50% SF-1202 d 30 Example 13 copolymer Polydimethylsiloxane fluid (pentamer) General Electric Company Kelco Div. Merk
35 The rating system is as follows. (=) Much poorer than control. (-) Poorer than control. 0 Control, same as. (+) Slightly better than control. (++) Much better than control. (+++) Superior to control. The above data shows that improved water resistance over the control formulation can be obtained with formulations comprising the copolymers of the present invention. The above mentioned patents are all hereby incorporated by reference. 40 Many variations of the present invention will suggest themselves to those skilled in this art in light of the above-detailed description. For example, instead of n-hexane, a wide variety of other aliphatic hydrocarbon solvents may be empolyed, including but not limited to isohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane and isomers thereof. Also, it is contemplated that nonlinear aliphatic hydrocarbon solvents can be employed in the practice of the present invention such as iso- 45 paraffinic solvents and other paraffin isomers. Further, the alkyl orthosilicate can be selected from methyl orthosilicate, propyl orthosilicate and n-butyl orthosilicate in addtion to ethyl orthosilicate. All such obvious modifications are within the full intended scope of the appended claims.
50 Claims
1. A liquid resinous copolymer of R3SiO0.5 and Si02 units wherein R is a monovalent hydrocarbon radical selected from the group consisting of alkyl radicals of 1-8 carbon atoms, alkenyl radicals, cycloalkyl rad- icals, mononuclear aryl radicals and haloalkyl radicals, prepared by a process comprising hydrolyzing a 55 hydrolyzable triorganosilane with an alkyl orthosilicate in the presence of water and a solvent comprising an aliphatic hydrocarbon of from 6 to 15 carbon atoms having an aromatic hydrocarbon content of less than 0.5 percent by weight based on the total weight of the solvent.
10 EP 0 555 050 A1
Acopolymeras defined in Claim 1 wherein R is a radical selected from the group consisting of ethyl, propyl, butyl, octyl, phenyl, naphthyl, xylyl, tolyl, benzyl, phenylethyl, vinyl, allyl, cyclohexyl, cycloheptyl, cyclo- hexenyl, chloromethyl, chloropropyl and dibromophenyl.
A copolymer as defined in Claim 1 or Claim 2 wherein said alkyl orthosilicate is selected from those of the formula R'OSi where R' is a lower alkyl radical or a lower hydroxy alkyl radical.
Acopolymeras defined in Claim 3 wherein said R' is a radical selected from the group consisting of methyl, ethyl, butyl, octyl and hydroxyethyl.
Acopolymeras defined in any preceding claim wherein said aliphatic hydrocarbon solvent is selected from the group consisting of hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tet- radecane, pentadecane, hexadecane, isohexane, isoheptane, isooctane, isononane, isodecane, isoun- decane, isododecane, isotridecane, isotetradecane, isopentadecane, isohexadecane, isomers thereof and mixtures of any of the foregoing.
Acopolymeras defined in any preceding claim wherein said aliphatic hydrocarbon solvent comprises iso- paraffinic solvents having from 6 to 15 carbon atoms.
A copolymer as defined in any preceding claim wherein said resinous copolymer comprises from about 0.5 to about 1.0 R3SiO0.5 units per Si02 units.
A process for preparing a resinous copolymer of R3SiO0.5 and Si02 units wherein R is a monovalent hy- drocarbon radical selected from the group consisting of alkyl radicals of 1-8 carbon atoms, alkenyl radicals, cycloalkyl radicals, mononuclear aryl radicals and haloalkyl radicals comprising hydrolyzing a hydrolyz- able triorganosilane with an alkyl orthosilicate in the presence of water, comprising carrying out the hy- drolyzation reaction in the presence of a solvent comprising an aliphatic hydrocarbon solvent of from 6 to about 15 carbon atoms having an aromatic hydrocarbon content of less than 0.5 percent by weight based on the total weight of said solvent, wherein said resinous copolymer is in the liquid form.
A personal care composition comprising an effective amount of a liquid resinous copolymer as defined in any one of Claims 1 to 7.
A composition comprising in solution : (a) from about 20 to about 60 weight percent of a liquid resinous copolymer of R3SiO0.5 and Si02 units wherein R is a monovalent hydrocarbon radical selected from the group consisting of alkyl radicals of 1-8 carbon atoms, alkenyl radicals, cycloalkyl radicals, mononuclear aryl radicals and haloalkyl radi- cals, prepared by a process comprising hydrolyzing a hydrolyzable triorganosilane with an alkyl ortho- silicate in the presence of water and a solvent comprising an aliphatic hydrocarbon of from 6 to 15 car- bon atoms having an aromatic hydrocarbon content of less than 0.5 percent by weight based on the total weight of the solvent; and (b) from about 80 to about 40 weight percent of an M-stopped or silanol end-stopped diorganopolysi- loxane fluid.
11 EP 0 555 050 A1
European Patent Number EUROPEAN SEARCH REPORT Application Office EP 93 30 0752
DOCUMENTS CONSIDERED TO BE RELEVANT Category Citation of document with indication, where appropriate, Relevant CLASSIFICATION OF THE of relevant passages to claim APPLICATION an<- C1.5 ) X GB-A-1 125 170 (GENERAL ELECTRIC COMPANY) 1-4,7,8 C08G77/06 A 10 C08L83/04 * page 1, line 38 - line 52 * * page 1, line 71 - page 2, line 11 * * page 2, line 30 - line 53; claims 1,3 *
D,X US-A-3 205 283 (F. J. M0DIC) 1-4,7,8, 10 * column 1, line 45 - line 16 * * column 2, line 30 - line 55 * * claims *
P.A W0-A-9 210 161 (THE PROCTER & GAMBLE 9,10 COMPANY) * claims 1,2,5,6 *
D,A US-A-2 814 601 (C. C. CURRIE ET AL.) 10 * claim 1 *
TECHNICAL FIELDS SEARCHED (Int. CI.S )
C08G C08L
The present search report has been drawn up for all claims Place of tearta D«i of cuapteUo* of Ike searck THE HAGUE 26 APRIL 1993 KANETAKIS I, CATEGORY OF CITED DOCUMENTS T : theory or principle underlying the invention E : earlier patent document, but published on, or X : particularly relevant if taken alone after the filing date Y : particularly relevant if combined with another D : document cited in the application document of the same category L : document cited for other reasons A : technological background O : non-written disclosure & : member of the same patent family, corresponding P : Intermediate document document
12